Method of treating filamentous materials



Patented Apr. 29, 1941 METHOD OF MATERIALS Jose B. Calva, St. Paul,

Minn, assignor of onethird to George W. Benz, St. Paul, Minn.

No Drawing. Original 1936, Serial No. 106,427.

application October 19,

Divided and this application February 24, 1941, Serial No. 380,378

. 1': Claims.

This invention relates to the treatment of filamentous materials, animal or vegetable, natural or artificial from natural or synthetic products, including the skins of animals commonly known as fur, hair or wool, to encase thefilaments without chemically modifying the parent substance, or to chemically modify such substance, to either permanently straighten or permanently curl the filaments, or to impart gloss, or finish, or to make them resistant to chemical or to mechanical action.

A very important phase of my invention is the formation of condensation products with the parent substance of the filaments with properly selected re-agents. The chemical mechanismis analogous to that of synthetic resin formation, but in this case, the active chemical functional groups of the parent substance of the filaments act asone of the condensation re-agents, while the-other is supplied according to requirements, fonproducing the desired effect, result or reaction wit hout materially destroying the physical stru ture of the filament itself.

Ibeliev e myself the first to coat or impregnate entous materials with artificial resins or oid products formed in situ, and this invenincludes impregnation or coating without gnation, or both, of natural or artificial iii A entous matter. In the case of hair or wool, eat with a substance which chemically reth the fibre substances of the hair, in-

g the keratin or amino-bearing material filament, to form therewith a permanent resin pr ct, or the like.

The irivention is applicable for the treatment of,tanned pelage such, for example, as that of to permanently straighten the wool. and give gloss andfinish so that the treated pelt can be used for making fur garments in imitation of other more expensive furs. Such straightening has heretofore been attempted but has not proved to be permanent, the wool again becoming curly or kinky after wetting. Previouslyto my invention, elforts were made merely to coat the fibres in an attempt to straighten them and keep them straightened, but the coating material had no permanence, since it merely formed an outer covering on the filaments, an

incomplete layer in most cases.

The value of bristles in brush making depends upon their stiifness or rigidity. Those bristles which are stifiest, are therefore the most marketable, and are used for tooth brushes, hair brushes, clothes brushes, etc. I have found it to so treat bristles as to increase their rigidity and to make marketable those which are today considered of inferior quality or as useless. Thus, by the use of my invention the inferior grades of bristles can be given the qualitiesof those of the finest natural product.

Hairs or similar fibrous materials are strongly attacked, even to the extent of being dissolved, by strong alkalies like caustic soda. I have found that by treatment of these fibrous materials in accordance with my invention, it is possible to make them generally more resistant to certain chemicals orto make them much less vulnerable to such, action.

The following filamentous substances can be treated by the practice of my invention: animal products or products derived therefromincluding hair, wool, silk, etc. artificial products, such as filamentous materials produced from collagen or its derivatives such as those made from glue, gelatin, as well as from casein, isinglass etc.; and filamentous materials derived from protein substances, such as catgut, etc.; also vegetable products, or products derived therefrom including natural fibres such as hemp, manila, jute, etc.; also roots, such as are used in the manufacture of brushes; and artificial vegetable filaments made from cellulose or cellulose hydrate, etc.

Various reactant substances may be used in carrying out the invention, and the only one example of the application of the principles in the treatment of tanned pelage such as that of the sheep, or other soft or hard fur, wool, hair or bristles, to straighten the wool or hair and impart a high gloss to it, and impart to it hydrophobic properties. The gloss isa function of the straightening. Brilliance, or gloss, is not usually obtainable when super-curling fur, because of the change in light reflecting properties, brought about by the physical structure produced.

possible by my process Example I The tanned and dried with a hydrocarbon solvent suchas petroleum, or benzol, or ethers, or chlorine-substituted hydrocarbons, or with any suitable degreasing or washing agent, after which the pelt may or may not be dried. The pelt is then soaked in water which completely penetrates the ually a properly selected substance which will penetrate the fibrous structure of the leather, and so coat it as to prevent following is pelt is optionally first degreased either by washing or by treatment leather and serves as a vehicle to draw thereinto,.uniformly and graddeleterious contact be at mummemwamrisandthm Wv i mflaeddeomomwmulmemmmwmmmmn matahl and! Mint! Asma- Imidmdot www- As lmemmmofispafis flttmwmmemu- 2 NIH-.13, m .,-:1|h flu Theufidis v -u ulwi nh w "H I as v'u' 'luhims the aria; M -va to a w the at v for Imam 15 to m In them the skim be to good .v'hllhlm the is the am flue exwashed and B: flnmput to soak for a m-mm m m the lvandlnvinga MMQtoWG, "Maths and it: a "m Ac-mum:

We! madam a m at? w ltistolm'm'gaafmwflflne '1. in" the am. ofi Minthis remdleneiisw imlbytmefiime wan-aimed fowmfiihmafiflm we The 02f stagfiwm hatfm ismwmely pmpontiitmwn to a-Mn" Tnetempemfiumofifim oi. the nezwli mts within: mentmustbe regulafiefltoflfine mm aw i the pezishalwe arm I me that trea: with hm men theimpnegnation, a. M, The explanation fat WES m motthewwuawhmw madtvehyflwm'mimiim solution, canbeeasfiymmm with a to am r to W611" mmam time ma saliva-madman withthemmt mist the w beatmrmmbolf mmmnssm- Kim is to the swelling at am w w- 'b IL Theismedto annals the' at any add may. .01? Aficrthealamwenggwhichv infertile offlmlast traces ofi millekwndwdwaifier. This washin; ii for be m M freeing the skinv from my salt has penetrated it 11m previ-- ms andwlficnhasmfmmdaat the acid-ambienflIE istofidmeofsadlium chloridizav mine skin is w warming, during;

e of the wooii 5mm be '10 and 110 C. This heat trearfl 'mmmm of the resinous or resiwmw woportiomll fie m and than. preparefi t'm De' noid condensation products which it is the object to produce. The combing operation thus carried out on the dry and chemically modified fibre assists in completing the condensation reactions which had been taking place at lower temperatures.

, Example II The following is especiallyrecommended for loose wooL bristles, or hair and consists in sub- 90 minutes. The resulting wool possesses gloss and is silky and free of kinks. The wool is removed from the autoclave and is washed thoroughly with water and then dried and heated if desired. Heating willincrease polymerization which results in further stiffening. This is an economical way of treating wool and has the advantage that the final product is completely free from odor. The last process, though most suitable for loose wool, can also be applied to tanned pelage, provided that a special tanning process such as'oil tanning or formaldehyde tanning has been used. Both processes are applicable to hair or bristles, in which case theefiect sought is not to straighten or impart lustre, since these two properties are already inherent in theproduct or material, but to make the keratin of which they are formed less susceptible to chemical reaction,

when brought in contact with strong alkalies or acids. This process is particularly advantageous for the treatment of bristles used in the manufacture of brushes.

The above process is applicable to loose wool or hair, or bristles. Whereshorn wool is being treated, the time of processing or the concentration of reagents can be somewhat increased. since there is no tanned skin structure to be preserved. Higher mechanical resistance, and improvement in other mechanical properties, such as rigidity, is obtained by additional polymerization. Similar results can be obtained by carrying out the same reaction at ordinary temperature and pressure for 24 to '72 hours, removing the fibrous materials from the formaldehyde solution and drying them at a temperature of about 100 C. The fibrous materials are then washed to free them of any water soluble substances and dried again.

Of the reacting substances which I have given in Example I, cresol, which is a hydroXy-aromatic compound, is useful in my invention. Cresol has only a limited solubility in water but is completely miscible in hydrocarbons and alcohol. Hydrochloric acid whose presence is also necessary for the reaction is only slightly soluble in hydrocarbons and in cresol, but is very soluble in water. Therefore, in order to make a homogeneous mixture of hydrochloric acid, hydrocarbon and cresol, it is desirable to use a fourth substance which may be termed a homogenizer. This homogenizer in this instance is alcohol. Between alcohol, benzol, and water, constant boiling point mixtures are formed of which the azeotropic mixture is an illustration. This azeotropic mixture will dissolve hydrochloric acid gas in sufficient amount for the purposes of this invention without suffering a disturbance of equilibrium. However, if

the maximum tolerance of this azeotropic mixture for hydrochloric acid gas is exceeded, the homogeneity of the mixture is destroyed and it separates into two layers, one composed mainly of hydrochloric acid and water and alcohol, and the other of benzol and alcohol.

The principal object in the preparation of this solution isto have a physically homogeneous mixture. The presence of water is required and the presence ofsome other reactants which are water-non-miscible 'is also required. For the proper mixing of these non-miscible substances a homogenizer is important. It is therefore necessary to have a liquid capable of dissolving both the catalyzer and the reactants. i

To straighten the wool or hair I carry out the reactionin the presence of an acid catalyst. For

example, I react the wool with a hydroxy-aromatic compound, such as cresol, in the presence of hydrochloric or sulphuric acid. If loose wool is being treated somewhat higher temperatures than those required for the treatment of pelage can be used without deleterious effects on the wool. Acfine fur like a beaver will not tolerate as high a temperature as a sheep skin, partly because of the thickness of the skin.

The results of the above, treatment will be a straightening of the wool with a simultaneous production of high gloss (for straightening). If the wool, mentioned above, is treated with a suitable reagent, at the proper temperature, in an alkaline medium, for example,' acetyl chloride in pyridine, Or even glacial acetic acid in pyridine the result will be a wool whose curl has been substantially increased (super curl). In this case, the amino groups of the keratinous material of fibre are acetylated.

My process may be applied to sheep wool to condition it for use in the manufacture of rugs giving the wool a gloss which is permanent, and also permanently straightening it, which conditions are not destroyed by water wetting. My treatment also renders the wool moth-proof. The invention therefore also includes the treatment of tanned sheep pelage for permanently modifying the chemical structure of the filaments.

The following is an example of the procedure for the formation of the condensat on products,

around, or to encase, an animal fibre, as distinguished from the utilization of the keratins of the fibre in the formation of such condensation products.

Example III The filamentous material after degreasing by any suitable means, as previously described, is coated with furfuryl alcohol as for example by dipping, and then allowing the excess of the alcoho] to drain off. The alcohol coated fibre is then either exposed to hydrogen chloride or dipped in a solution of hydrochloric acid of any concentration from 5 to 37%. By this process the furfuryl alcohol is transformed into a resinous substance formed in situ, which encases and adheres to the fibre. There apparently is no reaction in this case, between the material of the fibre, and the furfuryl alcohol or hydrochloric acid.

Example IV stance. In thi case; first either coat, or by al-,

lowing sumcient time impregnate the animal fibres with an aqueous solution of freshly made saligenin. The coated or impregnated fibres ,are then subjected to the action of gaseous a or are dipped in liquid ammonia. The fibres thus treated are dried. The resulting fibre will be either coated without penetration, or its structure will be penetrated by the resinous body, resultant from the reaction. This penetration is to be distinguished from coating without penetration which latter is also a feature of my invention. A to saligenin to be converted into a resinoid, requires the presence of an alkaline environment. Such an environment may be furnished by the kerat ous substance of the fibres, or by the action of ammonia without reaction with the parent sub- .1

stance of the fibre. The time required for penetration varieswith the type of fibre but can be accomplished within a period of about '72 hours. It is possible, by varying the time, to control the degree of penetration or entirely to prevent pene- 2m tration and simply coat the filament.

Furthermore, one of the reagents used in the formation of saligenin is formaldehyde, and this substance is present in excess or in equilibrium with phenol; in the freshly made siligenin reaction products. These two substances, phenol and formaldehyde also react with keratins giving rise to resinous substances.

The above example also includes the general type in which the fibre is coated by a resinoid.

formed in situ. Internally it has in its structure resinoid bodies, formed from saligenin, and keratin, the two having reacted to form the resinous substance.

In Example III, a mineral acid, hydrochloric acid was the catalytic agent for the res ction of resinification. In Example IV, a base, ammonia.

.was the catalytic agent inducing asimilar type of reaction. In the case of vegetable fibres, if

they are treated as in Example III, or as in Example IV, a definite change in the physical properties of the fibre results, due to the formation in situ of resinous bodies.

In carrying out the present invention I utilize the available reactive groups of the substances comprising the parent material being treated,; as starting materials in the formation of .resinoid materials. The types of reactions involved depend upon the substance being treated, that is to say, whether it is wool, hair, bristle, silk, glue,

gelatine, hemp, manila, jute, etc., and are illustrated by the following examples of resinoid formation: (l) Condensation of aromatic amines with aldehydes; (2) Condensation of amides and aldehydes; (3) Condensation of amino groups linked to carbonyl groups with aldehydes; i4) Condensation of amines with hydroxy-aromatic compounds; (5) Condensation of aldehydes with hydroxy-aromatic compounds; (6) Condensation of amino acids with aldehydes; (7) Condensation of proteinic'substances with aldehydes; i8) Condensation of proteinic substances with hydroxy-aromatic compounds; (9) Condensation oi aldehydes among themselves; and (10) Condensation and polymerization of unsaturated com- 5 pounds.

In the case where a chemical change of the parent substance of the fibrous material takes place, the change is obtained without destroying the filamentous structure, or form, and thus I to product hardly distinguishable, by the naked eye, 15

from hair. The is applicable for curling as wh and curling can be carried to apointw'h nthefinalproducthas a compact felted In the case or loose animal filamentous materials such. as hair. bristles or wool my process hnparts to them either or making them resistant to the action of d im illl arising hydrolytic. or hydrolizing agents. I am also able to produce products whichv are by the action of washing. and. which are indestructible by in sects. I am also able to increase diameter of the filament.

During the formation of the condensation product or products in the filament,

ing or curling or the isinduced, depeneting upon the reacting medium to form the condensation product. I do not intend. to be limited to the character of the or condensation. product is and which changes the character of the filament,v because I believe myself the first to of formation in situ, and the first toproduce a process wherein. thesubstance or the or vegetable matter itself is in formation of asynthetic: resin. or resinoid; substance,= formed either throughout any portion oh the sub stance of the filament or-in the outer or layer portion thereof, and first to form 9;.- permits nent combination. by a. process: in. which. condone sation, or even; further polymerization may occur. the caseof hair or the like, I thus change the: chemical structure of the keratinous,. amino-bearing filamentous material; The in.- vention contemplates the treatment of wool, fur, or bristles as well as: tanzncfii pelage.

for example of the sheep, to permanently straighten. the filaments for for garments or rugs or any other uses to which. the material may be Put. using the expressioom "in situ" I mean: distinguish from the separate making: of a res inoid substance and dissolving it suitable means and applying i'tto the fibers, and. then. subsequently eliminating or removing the solvent by physical. or chemicalv means; as for example. by dissolving; a or synthetic rain in a solvent which is later elinunated by evaporation. or by dissolving this resin or ISlIlOfti substance which with that chemical whose reaction product islater' broken up by use ot a third ireagent such, fbqtexample, as rosin soap, precipitateci' subsequently with an acid producing; sub-r stance.

It is understood that, the practice of my invention, the parent substance or) the fibre, animal or vegetable. made to react in various degrees with the treating reagent, or the resinoicl substance can be formed in situw'r'thout any 1% action involving utilization oi? substance 01 the fibre. some instances. there are reactions: in some no suriacereactions; in some. there is a. deeper amounting to inmregnation; and in some the reaction. may involve any selected portion of the I also materials of the above nature. animal or vegetable, after they have been; woven into ciotla,

and. my intention is to cover by claims; the application of my invention to the ofi woven goods, as as of ments whatever form theymaybe in.

My intention is to cover broadly the of fibrous materials, animal. or vegetable: natural or or made from natural orsynthetie products to form therewith or thereabout in situ a resinoid substance, whether involving the reaction of the parent substance or the fibre, or not involving such reaction of the parent substance. I also intend to cover all mechanisms and details herein disclosed, or inherent herein as ideas of means, or methods.

This application is a division of my application, Ser. No. 106,427, filed October 19, 1936.

I claim as my invention:

1. The method of treating animal furs which comprises subjecting the fur to a resinification agent in the presence of a catalyst at a moderate temperature and then continuing the resinification of the fur by mechanical finishing by combing at an elevated temperature.

2. The method of treating animal furs which comprises subjecting the fur to a resinification agent comprising formaldehyde in the presence of an acid catalyst and then continuing the resinification of the fur by mechanical finishing by combing at an elevated temperature.

3. The method of treating animal furs which comprises subjecting the fur to a resinification agent comprising formaldehyde in the presence of an acid catalyst and then continuing the resinification of the fur by mechanical finishing by combing at a temperature between 70 and 4. The method of treating animal furs to modify a selected portion of the fur filaments which comprises subjecting the selection portion of the fur filaments to a resinification agent and then continuing the resinification of said fur by mechanical finishing at an elevated temperature.

5. The method of treating anima1 furs to modify a selected portion of the fur filaments which comprises subjecting the fur filaments to a resinification sinification of the selected portions of said filaments at an elevated temperature.

6. The method of treating fine furs to improve the appearance and mechanical properties which comprises subjecting the fur to a resinification agent in the presence of a catalyst at a moderate temperature and then continuing the resinification of the fur by mechanical finishing at an elevated temperature.

7. The method of treating animal pelage having a natural filamentous covering thereon which comprises, subjecting the natural filamentous covering to a solution of resin-forming reactant capable of being adsorbed by the material, and to a reagent capable of forming resinous condensation products in situ with the resin-forming reactant and. with the thus treated filamentous coating, and of thereafter simultaneously mechanically treating and heating the filamentous material.

8. The process of treating animal pelage to decrease the tendency of the filamentous covering thereon to curl due to exposure to moisture which comprises impregnating the filamentous covering with an agent capable of resinification with formaldehyde and contacting the impregnated wool with formaldehyde to produce a substantially ent and then continuing the reof said fur by mechanical finishing.

. prises treating the water-insoluble compound, said reaction being effected in the presence of a catalyst.

9. The process of treating sheep skin to de-" crease the tendency of the wool thereon to curl due ,to exposure to moisture which comprises impregnating the wool with an agent capable of resinification with formaldehyde and contacting the impregnated wool with formaldehyde to produce a substantially water-insoluble compound, said reaction being eflected 10. The process of treating animal furs, particularly sheep skin, to decrease the tendency of the hair or wool thereon to curl due to exposure to moisture which comprises impregnating the furswith an amine and then contacting the impregnated fur with an aldehyde having the property of reacting with the amine to produce a substantially water-insoluble compound.

11. An animal fur, the hair or wool of which is relatively free from the tendency to curl due to exposure to moisture, said fur being impregnated with a substantially water-soluble reaction product of an aldehyde and an amine.

12. A dyed sheep skin, the wool of which is relatively free from the tendency to curl due to the presence of moisture, said sheep skin being impregnated with a substantially water-soluble reaction product of an aldehyde and an amine.

13. An animal fur, the hair of wool 01 which is relatively free from the tendency to curl due to exposure to moisture, said fur being impregnated with a resinous product of reaction of an aldehyde and a reagent capable of resinification with aldehydes, said resinous reaction product being formed in situ by application of said aldehyde and reagents to the fur or hair.

14. An animal fur, the hair or wool of which is relatively free from the tendency to curl due to exposure to moisture, said fur being impregnated with a resinous product of reaction of formaldehyde and an aromatic compound having a'substituent capable of resinification with formaldehyde, said resinous reaction product being formed in situ by application of said formaldehyde and aromatic compound to the fur or hair.

15. An animal fur, the hair or wool of which is relatively free from the tendency to curl due to exposure to moisture. said fur being impregnated with a resinous product of reaction of formaldehyde anda hydroxy aromatic compound, said resinous reaction product being formed in situ by application of said formaldehyde and aromatic compound to the fur or hair.

16. The process of treating animal pelage having a filamentous covering thereon which comprises treating the filamentous covering with furfuryl alcohol and exposing the thus treated filamentous covering to the action of an acid catalyst.

17. The process of treating animal pelage having a filamentous covering thereon which comfilamentous covering with an aqueous solution or saligenin and subjecting the thus treated filamentous covering to the action of a. basic catalyst.

JOSE B. CALVA.

in an acid medium 

